Apparatus for preparing a photoelectromotive force member having a concentric triplicate conduit for generating active species and precursor

ABSTRACT

An apparatus for the preparation of a photoelectric conversion layer for a photoelectromotive force member includes: 
     (a) a film-forming chamber having an inner space in which a substrate holder for a substrate is provided; 
     (b) an exhaust pipe connected to the film-forming chamber and through a main valve to an exhaust pump; 
     (c) a concentric triplicate conduit connected through a nozzle to the film-forming chamber. The concentric triplicate conduit includes: 
     (i) an outer passage for introducing a gaseous raw material and formed by a circumferential wall and an inner wall having a plurality of gas liberation holes; 
     (ii) a middle passage for applying microwave energy to said raw material gas to generate an active species and having a mixing region at the downstream side before the nozzle means, and 
     (iii) a central passage situated horizontally within said middle passage (ii) for introducing a gaseous precursor and for transporting the gaseous precursor toward the film-forming chamber and being open at its end positioned in the mixing region leaving a desired distance to the nozzle means; said middle passage (ii) being formed by the inner wall of the outer passage and a circumferential wall of the central psssage (iii). 
     Also included are: 
     (d) a feed pipe for introducing said raw material to said outer passage (i); 
     (e) a microwave power source for generating said microwave energy; and 
     (f) a feed pipe for introducing said gaseous precursor to said central passage (iii).

This is a division of application Ser. No. 843,304, filed Mar. 24, 1986now U.S. Pat. No. 4,689,093.

FIELD OF THE INVENTION

This invention relates to a photoelectromotive force member such asphotovoltaic members and the like and to a process and an apparatus forpreparing the same.

BACKGROUND OF THE INVENTION

There have been proposed a number of photoelectromotive force membershaving a photoelectric conversion layer composed of amorphous siliconfor use in photovoltaic devices and the like.

Various methods for preparing photoelectric conversion layers by meansof vacuum evaporation, thermal induced chemical vapor deposition, plasmachemical vapor deposition, reactive sputtering, ion plating and lightinduced chemical vapor deposition have also been proposed.

Among those methods, the method of thermal induced chemical vapordeposition (hereinafter referred to as "CVD method") had once beenfrequently used in various applications. However, such methods are notusually employed for the reason that, besides requiring an elevatedtemperature, a practically usable photoelectric conversion layer cannotbe obtained as expected.

On the other hand, the plasma chemical vapor deposition method(hereinafter referred to as "plasma CVD method") has been generallyevaluated as being the most preferred and is currently used to preparethe photoelectric conversion layer of photoelectromotive force memberson a commercial basis.

However, for any of the known photoelectromotive force members whichhave a photoelectric conversion layer composed of amorphous silicon,even if it is obtained by the plasma CVD method, there are stillunsolved problems regarding performance characteristics, particularlyits electric and optical characteristics, deterioration resistance, anduse environment characteristics upon repeated use, and also homogeneity,reproducibility, and mass-productivity.

Now, although the plasma CVD method is widely used nowadays as abovementioned, that method is problematical due to the fact that it ispracticed under elevated temperature conditions and other problems areassociated with the apparatus to be used.

Regarding the former problems, because the plasma CVD method ispracticed while maintaining a substrate at an elevated temperature,firstly the kind of a substrate to be used is limited to one that doesnot contain a material such as a heavy metal which can migrate and causechanges in the characteristics of a deposited layer to be formed andsecondly, its thickness is likely to be varied, whereby the resultinglayer lacks uniformity of thickness and homogeneity of the composition,which may itself also cause changes in the characteristics of the layerto be formed.

Regarding the latter problems, the operating conditions employed withthe plasma CVD method are much more complicated than the known CVDmethod, and are extremely difficult to be generalized.

That is, there already exist a number of variations even in thecorelated parameters of substrate temperature, the amount and the flowrate of gases to be introduced, the pressure, the high frequency powerfor forming a layer, the structure of the electrodes, the structure ofthe reaction chamber, the exhaust rate, the plasma generation system,etc. Under these circumstances, in order to prepare a desirablephotoelectric conversion layer for a photoelectromotive force member, itis required to choose precise parameters from a great number of variedparameters. And there sometimes occurs a serious problem that because ofthe precisely chosen parameters, the plasma may attain an unstable statewhich often imparts unexpected troublesome effects to a photoelectricconversion layer to be formed.

As for the plasma CVD apparatus, its structure becomes complicatedbecause the parameters to be employed are precisely chosen as abovestated, and whenever the scale or the kind of the apparatus to be usedis modified or changed, the apparatus must be so structured as to stillprovide said precisely chosen parameters.

In this regard, even if a desirable photoelectric conversion layershould be fortunately produced, the photoelectromotive force memberproduct will become costly for the reasons that a heavy investment isnecessitated to set up a particularly appropriate apparatus therefor.Then, as there still exist a number of process operation parameters evenfor such an apparatus, the relevant parameters must be precisely chosenfrom the existing various parameters for the preparation of such adesirable photoelectric conversion layer, and thus the process must becarefully practiced.

Against this background, there is now an increased demand for providinga method that makes it possible to practice the process at lowertemperature and at a high film forming rate in a simple apparatus tomass-produce a desirable photoelectric conversion layer for aphotoelectromotive force member which has good uniformity and haspractically applicable characteristics.

Besides silicon, there is a similar situation with respect to otherkinds of photoelectric conversion layers for photoelectromotive forcemembers such as silicon nitride, silicon carbide, and silicon oxidelayers.

SUMMARY OF THE INVENTION

The present inventors have conducted extensive studies in order to solvethe problems in the aforementioned known methods and in order to developa new process for effectively and simply preparing a photoelectromotiveforce member having a desirable photoelectric conversion layer, forinstance, an amorphous silicon layer having practically applicablecharacteristics.

As a result, the present inventors have finally found a method thatenables efficient and stable preparation of a desirable photoelectricconversion layer for photoelectromotive force member according to thesimplified procedures detailed below.

It is therefore an object of this invention to provide an improvedphotoelectromotive force member having a desirable photoelectricconversion layer having practically applicable characteristics, which isprepared by chemically reacting a precursor contributing to form saidphotoelectric conversion layer and an active species without the use ofplasma discharge.

Another object of this invention is to provide a new process forpreparing the above photoelectric conversion layer using a precursorcontributing to form the layer and an active species which can bechemically reacted at lower temperature and without the presence of aplasma to form the layer on a substrate for a photoelectromotive forcemember located in a reaction space of a closed system at a highdeposition rate.

A further object of this invention is to provide an apparatus suitablefor practicing said new process.

According to one aspect of this invention, the new process aims ataccomplishing simplification of the layer forming conditions for thepreparation of a photoelectric conversion layer so as to enable itsmass-production while maintaining the characteristics of the layer to beformed and promoting the deposition rate at lower temperature in adeposition space without using a plasma reaction.

According to a further aspect of this invention, there is provided animproved photoelectromotive force member having a desirablephotoelectric conversion layer which is prepared by introducing aprecursor contributing to form the above layer and an active specieswhich is chemically reactive with the precursor into a deposition space,the active species being passed through a transportation space leadingto the deposition space and the precursor being passed through an othertransportation space leading to the deposition space which is providedwithin the foregoing transportation space, and chemically reacting thetwo substances at lower temperature in the deposition space.

According to a further aspect of this invention, there is provided aprocess for preparing a desirable photoelectric conversion layer for aphotoelectromotive force member, characterized in that a precursorcontributing to form the layer and an active species chemically reactivewith the precursor are used together, wherein the active species ispassed through a transportation space of which the downstream side leadsto a deposition space, the precursor is passed through anothertransportation space leading to the deposition which is provided withinthe foregoing transportation space, and the two substances thusintroduced are chemically reacted to form the layer on a substrate forthe photoelectromotive force member placed in the deposition space, inthe absence of a plasma and without elevating the substrate temperature.

In accordance with an additional embodiment a process is provided forpreparing a photoelectromotive force member comprising: a photoelectricconversion layer on a substrate employing (i) a precursor as aconstitutent for the photoelectric conversion layer, which precursor issubstantially nonreactive as long as it remains in its original energystate and (ii) an active species which can react with and impart energyto the precursor to activate the precursor to a state capable ofcontributing to formation of said layer which comprises:

(a) generating said active species by subjecting a substance capable ofbeing activated to generate said active species to the action ofmicrowave energy in an active species generating and transporting spaceleading to a film forming space containing the substrate;

(b) simultaneously generating said precursor by subjecting a substancecapable of generating precursor to the action of microwave energy in aprecursor generating and transporting space located separately from andwithin the active species generating and transporting space and open ina downstream region of that space; and

(c) introducing the resulting active species and precursor into the filmforming space to chemically react them to form the photoelectricconversion layer on the substrate in the absence of a plasma.

According to a further aspect of this invention, an apparatus isprovided which is suitable for practicing the above process,characterized in that an active species generation space, an activespecies transportation passage being situated at the downstream side ofthe active species generation space, a precursor generation space, aprecursor transportation passage being situated separately from andwithin the active species transportation passage and a depositionchamber having a substrate supporting means therein, are provided.

According to this invention, since a precursor contributing to form adeposited film and an active species chemically reactive with theprecursor even at lower temperatures are used, there is no particularlimitation on the kind of substrate to be used as in the known plasmaCVD method, and the formation of a desirable photoelectric conversionlayer on a substrate for a photoelectromotive force member may beeffectively carried out at a high deposition rate without elevating thetemperature of the substrate, namely from 80° to 120° C. lower than inthe known plasma CVD method, and moreover, in the absence of a plasma.

In addition, according to this invention, the control of the layerforming conditions is relaxed and quality control of a layer to beformed can be easily implemented because the deposition space issituated separately from the space for generating the precursor and fromthe space for generating the active species, the former space and thelatter spaces being separate from one another, and a plasma discharge isnot utilized.

In this invention, an active species and a precursor are respectivelyintroduced into a film forming space through an active speciestransportation space and a precursor transportation space. It ispossible to optionally determine the residence time for the precursorwithin the precursor transportation space by appropriately changing thelocation of its open portion within the active species transportationspace, wherein the transportation rate of the precursor in the precursortransportation space may be chosen as one of the variable parameters tocontrol the residence time.

The position where the precursor transportation space and the activespecies transportation space opens to the deposition space may bedetermined with due regard to the life span of the active species and tothe life span of the precursor.

As for the position of the active species transportation space whichopens to the deposition space, it is preferred to be as close aspossible to the layer forming region in the deposition space since thereare generally used a precursor of a relatively long life span and anactive species of a rather shorter life span.

The portions of the active species transportation space and theprecursor transportation space which open to the deposition space arepreferably in the form of a nozzle or an orifice.

And, particularly when both the open portions are in the form of anozzle, the layer forming and feed consumptive efficiencies may beremarkably improved by situating the nozzle openings at a closerposition to the layer forming surface of the substrate in the depositionspace.

In general, the active species is generated in a species activationspace connected to the active species transportation space at itsupstream portion, and the precursor is generated in a precursorgeneration space connected to the precursor transportation space at itsupstream portion.

However, as an alternative, both the active species transportation spaceand the precursor transportation space may be so structured as to doublerespectively as the active species generation space and the precursorgeneration space.

In that case, the active species generation means and the precursorgeneration means need not always be separately provided. The relatedsystem may be so structured that a sole means serves both as the activespecies generation means and the precursor generation means. As anexample in this respect, there can be illustrated a double conduit suchas a double glass pipe which is structured to have an inner passage asthe active species transportation space and an outer passage as theprecursor transportation space. In this case, there is placed amicrowave power source around the circumference of the double conduit soas to generate at the same time an active species and a precursor flowin the direction of the gas current. The open portion of each of theactive species transportation space and the precursor transportationspace is preferred to be situated within the deposition space.

The number of double space structural conduits having the precursortransportation space horizontally situated within the active speciestransportation space, which is connected to the deposition space, is notlimited to be one but may be pluralized.

In the latter case, a photoelectric conversion layer constituted by aplurality of active layers, each having a different characteristic, maybe formed on a substrate for a photoelectromotive force member placedwithin the deposition space, by changing the kind of active speciesand/or the kind of precursor introduced through each of the double spacestructural conduits.

In that case, it is possible to simultaneously start forming each of theactive layers on a respective position of the substrate. It is alsopossible to form such a multilayered film as having various activelayers, for example, (A) to (N) layers by firstly forming the (A) layer,then the (B) layer, . . . and finally the (N) layer.

As a more detailed example, when a photoelectric conversion layer of aphotoelectromotive force member having an n-type semiconductive layer,an i-type semiconductive layer, and a p-type semiconductive layer inthis order from the side of the substrate is desired, it may be preparedby using three said double space structural conduits in the followingway. That is, the n-type semiconductive layer is firstly formed on thesubstrate by using the first conduit, the i-type semiconductive layer isthen formed on the n-type semiconductive layer already formed on thesubstrate by using the second conduit, and the remaining p-typesemiconductive layer is finally formed on the n-type semiconductivelayer by using the third conduit.

In this case, the formation of each of the three layers on the substratemay be carried out in the same deposition space by starting theformation of a successive layer after the formation of the former layerhas been completed. And in another alternative of this case, theformation of each of the three layers may be carried out in concurrentprogression of time simply by letting the starting time for theformation of each layer be delayed a predetermined time period, althoughthere is somewhat of a local delay in the formation of each layers.

In this invention, it is a matter of course that the formation of eachlayer in the above case may be carried out in a different depositionspace.

However, in the above case the most characteristic point of thisinvention is that multiple layers, each of which has a differentcharacteristic, is formed in concurrent progression on a substrate for aphotoelectromotive force member in the same deposition space.

Further, according to this invention, there are the advantages accruingfrom the formation of a photoelectric conversion layer of aphotoelectromotive force member without elevating the temperature of thesubstrate and in the absence of plasma, this being distinguished fromthe case of the known plasma CVD method. For example, a desirablephotoelectric conversion layer having a uniform thickness and adesirable homogeneity may be effectively formed at an improveddeposition rate without the formed layer peeling off from the substrate,which often found in the known plasma CVD method when it is practicedwith the substrate being maintained at lower temperature, and the layerwhich is formed on the substrate is not affected either by any of theundesirable materials removed from the inner surface of the surroundingwall of the deposition space or by the residual gases remaining in thedeposition space, because the deposition space, the active speciesgeneration space, and the precursor generation space are individuallysituated.

The term "precursor" in this invention means a substance which can be aconstituent of a photoelectric conversion layer of a photoelectromotiveforce member but cannot contribute to layer formation as long as it isin its usual or "ground level" energy state.

On the other hand, the term "active species" in this invention means asubstance which causes a chemical reaction with the precursor to impartenergy to the precursor thereby to cause the precursor to be in anactivated energy state capable of contributing to formation of saidlayer.

Therefore, as for the active species to be used, it may be either asubstance which contains one or more elements which are constituents ofthe desired photoelectric conversion layer of the photoelectromotiveforce member to be formed or a substance which does not contain suchelements.

The precursor which is introduced into the deposition space through theprecursor transportation space will become a principal constituent ofthe photoelectric conversion layer to be formed on the substrate forphotoelectromotive force member in the deposition space. The longer theaverage life span of the precursor the better. A substance whose averagelife span is preferably greater than 0.01 second, more preferablygreater that 0.1 second and most preferably greater than 1.0 second isused.

The active species to be introduced into the deposition space throughthe active species transportation space should be a substance whoseaverage life span is preferably less than 10 seconds, more preferablyless than 8.0 seconds, and most preferably less than 5.0 seconds.

At the time when a photoelectric conversion layer is formed on asubstrate for the photoelectromotive force member in the depositionspace, the active species chemically reacts with the precursorcontaining one or more elements to be principal constituent(s) of thelayer be formed. The precursor is introduced into the deposition spaceat the same time when the active species introduced thereinto throughthe active species transportation space, whereby the desired film iseasily and effectively formed on the substrate.

According to this invention, because the photoelectric conversion layermay be formed without any generation of a plasma in the depositionspace, there is no occasion for the layer to be subjected to theinfluence of an etching action or other actions due to unexpectedlyoccurring abnormal discharge and the like during its formation, as foundin the known plasma CVD method.

The process for forming the photoelectric conversion layer of aphotoelectromotive force member according to this invention is amodification of the known CVD method, and in order to be distinguishedfrom the known CVD method, it will be appropriate to be categorized asthe "New CVD method."

One remarkable point among others by which the New CVD method of thisinvention is clearly distinguished from the known CVD method is thatthere is used an active species which is generated in a space separatelysituated from the deposition space.

Because of this, this invention brings about various significantadvantages such that in comparison with the known plasma CVD method, thedeposition rate is greatly improved and at the same time, aphotoelectric conversion layer superior in quality and having verystable characteristics may be obtained. In addition, the temperature ofa substrate for the photoelectromotive force member is much lower thanin the case of the known plasma CVD method when a photoelectricconversion layer is formed thereon, and a photoelectric conversion layerpossessing excellent characteristics may be mass-produced on anindustrial scale thereby enabling low cost production.

The active species to be used in this invention is generated in theactive species generation space by activating a selected raw material togenerate the active species, for example, by subjecting it to the actionof an excitation energy source such as electric discharge, light, heat,or by reacting or contacting it with a catalyst or by adding thecatalyst thereto.

Usable as the raw material are, for example, H₂, SiH₄, SiH₃ F, SiH₃ Cl,SiH₃ Br, SiH₃ I, etc., and other than these, rare gases such as He, Ne,Ar, etc. are also usable.

A suitable compound is used for the generation of the precursor to beused in this invention.

As such a compound, there is usually used a silicon containing compoundin which an electron highly absorptive atom or atomic group or a polarradical is bonded to the silicon atom.

Said silicon containing compound is subjected to the action of anexcitation energy source such as electric discharge, light, or heat togenerate the precursor in the precursor generation space.

Usable as the silicon containing compound are, for example, Si_(n)X_(2n+2) (n=1,2,3---, X=F, Cl, Br, I), (SiX₂)_(n) (n≧3, X=F, Cl, Br, I),Si_(n) HX_(2n+1) (n=1,2,3---, X=F, Cl, Br, I), Si_(n) H₂ X_(2n)(n=1,2,3---, X=F, Cl, Br, I), etc.

Specific examples are SiF₄, (SiF₂)₅, (SiF₂)₆, (SiF₂)₄, Si₂ F₆, SiHF₃,SiH₂ F₂, SiCl₄, (SiCl₂)₅, SiBr₄, (SiBr₂)₅, etc. which are in the gaseousstate or can be easily made to be in the gaseous state.

Other than these compounds, SiH₂ (C₆ H₅)₂, SiH₂ (CN)₂, etc. may be alsoused in accordance with the intended use of the photoelectric conversionlayer to be formed.

In a preferred embodiment of this invention, the precursor and theactive species are well mixed in advance before being introduced intothe deposition space. Soon after the mixture is introduced into thedeposition space, if necessary, it is possible to apply light or heatenergy to the inner atmosphere of the deposition space where the layerforming process is to be conducted or to the substrate placed in thedeposition space and on which a photoelectric conversion layer is to beformed, thereby to further promote the deposition rate and toefficiently accomplish the layer formation.

The volume ratio of the precursor to the active species may bedetermined with due regard to the layer forming conditions, the kind ofprecursor to be used and the kind of active species to be used etc., butit is preferably 100:1 to 1:100 and more preferably 10:1 to 1:10 on thebasis of a flow amount ratio.

The position of the precursor transportation space opening in the activespecies transportation space is situated preferably 0.1 mm to 200 mm,more preferably 1.0 mm to 100 mm distant from the position of the activespecies transportation space opening to the deposition space.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1(A) is a cross sectional view of a first representative embodimentof the photoelectromotive force member for a photovoltaic deviceprovided according to this invention.

FIG. 1(B) is a cross sectional view of a second representativeembodiment of the photoelectromotive force member for a photovoltaicdevice provided according to this invention.

FIG. 1(C) is a cross sectional view of a third representative embodimentof the photoelectromotive force member for a photovoltaic deviceprovided according to this invention.

FIG. 2, FIG. 3, and FIG. 4 are schematic diagrams of apparatusessuitable for carrying out the process for preparing a photoelectromotiveforce member according to this invention.

DESCRIPTION OF THE PREFERRED EMBODIMENT

Referring to FIG. 1, photoelectromotive force member 100 is usable as aphotovoltaic device, and has a structure composed of p-type (or n-type)semiconductive layer 102, i-type semiconductive layer 103, n-type (orp-type) semiconductive layer 104, and electroconductive layer 105 onsubstrate 101.

Substrate 101 may be electroconductive or electrically insulating.

Usable as an electroconductive substrate are, for example, metals suchas Al, Cr, Mo, Au, Ir, Nb, Ta, V, Ti, Pt, Pd and the like, or alloyssuch as NiCr, stainless steel, or alloys of said metals.

Usable as an electrically insulating substrate are, for example, filmsor sheets of synthetic resin such as polyester, polyethylene,polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride,polyvinylidene chloride, polystyrene, polyamide and the like, and otherthan these, glass or ceramics. For the electrically insulatingsubstrate, it is desirable that at least one surface thereof be madeconductive and the relevant layers are formed on the conductive surfaceof the substrate.

For example, in the case of glass, its surface may be made conductive bydepositing a thin layer of metal such as NiCr, Al, Cr, Mo, Au, Ir, Nb,Ta, V, Ti, Pt, Pd, or a metal oxide such as In₂ O₃, SnO₂, ITO (In₂ O₃+SnO₂) etc. In the case of synthetic resin film such as polyester filmetc., its surface may be made conductive with a metal such as NiCr, Al,Ag, Pd, An, Ni, Au, Cr, Mo, Ir, Nb, Ta, V, Ti, Pt, etc. by means ofvacuum vapor deposition, electron beam vapor deposition, or sputtering.Its surface may also be made conductive by laminating it with one ofsaid metals.

The shape of the substrate may be optionally determined. Examples aredrum, belt, plate and suitable like shapes.

The thickness of the substrate is optional, but it is usually not lessthan 10 microns from the view points of its manufacturing and handlingconveniences and its strength.

Substrate 101 may be either transparent or opaque. In the case whensubstrate 101 is transparent, electroconductive layer 105 may be opaqueand the radiation of light is conducted from the side of substrate 101as shown in FIG. 1(A). In the case when substrate 101 is opaque,electroconductive layer 105 should be of an optically transparentmaterial and the radiation of light is conducted from the side ofelectroconductive layer 105 as shown in FIG. 1(B).

The p-type semiconductive layer 102 is composed of an amorphous materialsuch as an a-Si (H, X) containing silicon and at least one of hydrogen(H) and halogen atoms (X), and which has been doped with a p-typeimpurity to be of p-type.

It is desirable fof the p-type semiconductive layer 102 to be band-gapwidened so as to exhibit a so called window effect by adding a band gapincreasing element such as carbon, oxygen, nitrogen, or the like.

As the p-type impurity, there may be used an element of Group III A ofthe Periodic Table such as B, Al, Ga, In, Tl or the like. Of thesep-type impurities, B and Ga are the most appropriate.

The amount of the p-type impurity to be contained in the p-typesemiconductive layer 102 may be optionally determined in accordance withits end use, but it may be less than 3×10⁻² atomic %.

The process of doping the p-type semiconductive layer 102 with theseimpurities may be practiced by introducing a dopant imparting substancein the gaseous state into either the active species generation space orthe precursor generation space possibly together with a gaseoussubstance to generate a precursor or a gaseous stock so as to generatean active species when the layer is being formed.

As a dopant imparting substance capable of incorporating the impuritiesinto the layer, a substance which is in a gaseous state at roomtemperature or another substance which can be easily made to be in agaseous state, at least under the layer forming conditions, may beemployed.

Usable as such substance are, for example, BiH₃, BF₃, BCl₃, BBr₃, B₂ H₆,B₄ H₁₀, B₅ H₉, B₅ H₁₁, B₆ H₁₀, B₆ H₁₂, AlCl₃, etc.

The formation of the p-type semiconductive layer 102 may beindependently carried out, however, it is possible to continuously formthe i-type semiconductive layer 103 and the n-type semiconductive layer105 following the formation of the p-type semiconductive layer 102.

In the formation of p-type semiconductive layer 102, a gas for formingthe p-type semiconductive layer may be mixed with a rare gas such as Heand Ar in a predetermined volumetric mixing ratio when necessary.

In this invention, the formation of the p-type semiconductive layer 102may be carried out, for example, in the following way.

First an active species raw material gas is introduced into theactivation space, to which a relevant activation energy is appliedthereby to form an atmosphere containing active species generatedtherein, which is then passed through the active species transportationspace.

In parallel with this, a precursor raw material gas is introduced intothe precursor generation space to which a relevant activation energy isapplied thereby to generate a precursor, which is then passed though theprecursor transportation space situated within the active speciestransportation space.

The gas containing active species and the gas containing precursors aremixed in a mixing space situated in the active species transportationspace wherein the two substances will start chemically reacting, and theresulting gas mixture is then introduced into the film forming space,where the substrate 101 is placed, whereby the p-type semiconductivelayer 102 is formed on the substrate 101. In this case, if necessary,energy may be applied to the inner atmosphere and/or the substrate 101in order to further promote the deposition rate.

Usable as the above active species raw material for the formation of thep-type semiconductive layer are, for example, silane compounds abundantin hydrogen atoms, which are in the gaseous state or can be easily bemade to be the gaseous state, such as SiH₄, SiH₃ Cl, SiH₃ F, SiH₃ Br andthe like, nitrogen (N₂) or nitrogen compounds composed of nitrogen (N)and hydrogen atoms (H), which are in the gaseous state or can be easilymade to be in the gaseous state, such as nitrides and azides such asNH₃, H₂ NNH₂, HN₃, NH₄ N₃ and the like, others than these, saturatedhydrocarbons having 1 to 5 carbon atoms, ethylenic hydrocarbons having 2to 5 carbon atoms, and acetylenic hydrocarbons having 2 to 4 carbonatoms.

As the saturated hydrocarbons, there may be illustrated CH₄, C₂ H₆, C₃H₈, n-C₄ H₁₀, and C₅ H₁₂. As the ethylenic hydrocarbons, there may beillustrated C₂ H₂, C₃ H₄, and C₄ H₆. And as the acetylenic hydrocarbons,there may be illustrated C₂ H₂, C₃ H₄, and C₄ H₆.

In addition to these, the following are also usable as the activespecies raw material: O₂, O₃, CO, CO₂, NO, NO₂, N₂ O and the like.

The active species raw material to be used for the formation of thep-type semiconductive layer 102 is appropriately selected from thoseabove illustrated and used so that a predetermined atom contained in theselected raw material may be sufficiently incorporated into the p-typesemiconductive layer 102 to be formed.

As the precursor raw material used to generate a precursor in theprecursor generation space, silane compounds such as SiF₄, SiH₂ F₂ andthe like may be illustrated, and these substances may easily generateprecursors of a long average life span with the action of appropriateactivation energy.

The thickness of the p-type semiconductive layer 102 is preferably 30 to50,000 A, more preferably 50 to 5000 A and furthermore preferably 50 to1000 A.

The i-type semiconductive layer 103 is to be structured so as to havephotoconductive characteristics sufficient to function as the i-typesemiconductive layer of the photoelectromotive force member. Inconsequence, the i-type semiconductive layer 103 is preferably composedof an amorphous silicon a SiX (H) containing silicon as a maincomponent, halogen (X), and if necessary hydrogen (H).

The formation of the i-type semiconductive layer 103 may be conducted inthe same way as the formation of the p-type semiconductive layer 102.That is, an active species raw material such as SiH₄, SiH₃ F or the likeis introduced into the activation space to which a appropriateactivation energy is applied thereby to generate an active species,which is then passed through the active species transportation space. Inparallel with this, a precursor raw material such as SiF₄, SiF₂ H₂ orthe like is introduced into the precursor generation space to which anappropriate activation energy is applied thereby to generate aprecursor, which is then passed through the precursor transportationspace situated within the active species transportation space.

The gas containing active species and the gas containing precursors aremixed in a mixing space situated in the active species transportationspace wherein the two substances start chemically reacting, and theresulting gas mixture is introduced into the film forming space, wherethe substrate 101 is placed, whereby the i-type semiconductive layer 103is formed on the substrate 101.

Also in this case, if necessary, energy may be applied in order tofurther promote the deposition rate. As a result, a suitable i-typesemiconductive layer 103 is formed.

The thickness of the i-type semiconductive layer 103 may be determinedin accordance with its end use purpose.

As for the i-type semiconductive layer 103 of the photoelectromotiveforce member 100 or 106 as shown in FIG. 1(A) or FIG. 1(B),respectively, its thickness may be determined in relationship to thethickness of the p-type semiconductive layer 102 and the thickness ofthe n-type semiconductive layer 104 and also from the quantitativerelationship between the amount of the impurities with which the p-typesemiconductive layer 102 is doped and the amount of the impurities withwhich the n-type semiconductive layer 104 is doped so as to optimizeeach of the functions of the three layers concerned. However, in theusual case, the thickness of the i-type semiconductive layer ispreferred to be several times to several tens of times as much as thatof the p-type semiconductive layer 102 or that of the n-typesemiconductive layer 104, preferably 100 A to 10 μm and more preferably0.1 to 1.0 μm.

The n-type semiconductive layer 104 of the photoelectromotive forcemember 100 or 106 as shown in FIG. 1(A) or FIG. 1(B) respectively, maybe formed in the same way as the p-type semiconductive layer 102 or thei-type semiconductive layer 103 except that a different impurity is usedtherein.

As the impurity with which the n-type semiconductive layer 104 is doped,there may be illustrated, for example, elements of Group VA of thePeriodic Table such as N, P, As, Sb, Bi and the like. Of theseimpurities, As, P, and Sb are the most appropriate.

In order for the n-type semiconductive layer 104 to have the desiredtype of conductivity, the amount of the impurity with which the layer isdoped may be determined appropriately depending upon its desiredelectrical and optical characteristics.

In the case of impurities from the Group VA of the Periodic Table, theamount may be less than 5×10⁻³ atomic %. The doping of the n-typesemiconductive layer 104 with said impurity may be conducted byintroducing a dopant imparting substance in the gaseous state intoeither the active species generation space or the precursor generationspace possibly together with a gaseous substance to generate a precursoror a gaseous stock so as to generate an active species when the layer isbeing formed.

As the dopant imparting substance capable of incorporating the impurityinto the n-type semiconductive layer 104, a substance which is in agaseous state at room temperature or another substance which can beeasily made to be in a gaseous state, at least under the layer formingconditions, may be employed.

Usable as such substance are, for example, PH₃, P₂ H₄, PF₃, PF₅, PCl₃,AsH₃, AsF₃, AsF₅, AsCl₃, SbH₃, SbF₅ etc.

The total amount of H and X (X=halogen atom such as F) to be containedin each of the semiconductive layers of the photoelectromotive forcemember as shown in FIG. 1 is preferably 1 to 40 atomic %, and morepreferably 5 to 30 atomic %. For the amount of H itself, its lowestlimit is 0.001 atomic %, and it is preferably a 0.01 atomic %, and morepreferably a 0.1 atomic %.

The electroconductive layer 105 may be of either transparent or opaquematerial. Particularly when the substrate 101 is opaque as shown in FIG.1(B) and the light radiation is incident from the side ofelectroconductive layer 105, it is necessary for the electroconductivelayer 105 to be optically transparent or nearly so in order for thephotoelectromotive force member to exhibit a sufficient photoelectricconversion effect.

As the transparent electroconductive material to form theelectroconductive layer 105, there may be illustrated metal oxides suchas In₂ O₃, SnO₂, and ITO (In₂ O₃ +SnO₂), and metals such as Pd, Pt, Cu,Ag, Au, and Al. As opaque electroconductive materials to form theelectroconductive layer 105, there may be illustrated alloys such asNiCr, and metals such as Al, Cr, Mo, Au, Ir, Nb, Ta, V, Ti, Pt, Pd, Zn,and Ag.

The formation of the electroconductive layer 105 using these materialsmay be conducted by means of vacuum vapor deposition, electron beamvapor deposition or sputtering.

Since light is absorbed very effectively by the i-type semiconductivelayer 103, the foregoing p-type semiconductive layer 102 of the n-typesemiconductive layer 104 when situated on the side on which a light isincident is preferred to be of wider band-gap than the i-typesemiconductive layer 103.

For example, in the case when the p-type semiconductive layer or then-type semiconductive layer is desired to be a silicon carbide layer,SiH₄ and CH₄ and H₂, or SiH₄ and SiH₂ (CH₃)₂ are introduced into theactivation space to which an suitable activation energy is applied,thereby to generate an active species. In parallel with this, aprecursor raw material substance such as SiF₄ or the like is introducedinto the precursor generation space to which a suitable activationenergy is applied, thereby to generate a precursor. After this, inaccordance with the procedures as above mentioned, the active speciesand the precursor are mixed and then introduced into the depositionspace while they are chemically reacted, whereby the p-typesemiconductive layer or the n-type semiconductive layer to be situatedon the side on which light is incident is formed on the substrate 101.

As an alternative, the semiconductive layer of wider band gap than thei-type semiconductive layer 103 may be formed by introducing SiF₄ gastogether with CF₄ gas of C₂ F₆ gas into the precursor generation spaceto generate a precursor containing a carbon atom by means of anactivation energy applied thereto, mixing it with an active speciescontaining a hydrogen atom, and introducing the gaseous mixture into thedeposition space while being chemically reacted. In this case, a dopantimparting gaseous substance may be added to either the precursor rawmaterial gaseous substance or the active species raw material gaseoussubstance.

Regarding the photoelectromotive force member 107 of FIG. 1(C) providedaccording to this invention, it has a structure composed ofphotoconductive layer 103 and metallic layer 108, an optional insulatinglayer 109, and a substrate 101.

As the substrate 101, those as above mentioned may be used. Thephotoconductive layer 103 may be formed in accordance with the sameprocedures as in the cases of FIG. 1(A) or FIG. 1(B).

For the metallic layer 108, a metal such as Au, Pt, Pd or the like whichhas a large work function is used in order to make a Schottky contactwith the photoconductive layer 103. The formation of the metallic layer108 on the substrate 101 may be conducted by means of vacuum vapordeposition or electron beam vapor deposition.

The thickness of the metallic layer 108 is preferred to be less than 500A, because light passes to photoconductive layer 103 through metalliclayer 108.

The insulating layer 109 is provided to enhance the barrier between thephotoconductive layer 103 and the metallic layer 108. Therefore it isnot always necessary. The thickness of the insulating layer 109 may beextremely thin, for example, less than 2000 A.

In the case when the insulating layer 109 is provided in thephotoelectromotive force member 107, it is preferred to be of wideband-gap.

The formation of the insulating layer 109 may be conducted by adding agas containing a nitrogen source such as N₂, NH₃, NO, or NO₂, a gascontaining an oxygen source such as O₂ or CO₂, or a gas containing acarbon source such as CF₄, C₂ F₆, or CH₄ to a precursor raw materialgaseous substance or an active species raw material gaseous substance.

PREFERRED EMBODIMENT OF THE INVENTION

The advantages of this invention are now described in more detail byreference to the following Examples, which are provided merely forillustrative purposes only, and are not intended to limit the scope ofthis invention.

EXAMPLE 1

In accordance with the procedures described below, a photoelectromotiveforce member for a PIN type solar cell was prepared by using anapparatus as shown in FIG. 2.

In FIG. 2, 201 stands for a film forming chamber having inner space A inwhich a substrate holder 214 for substrate 207 having electric heater208 connected to a power source (not shown) by means of lead wires209,209 is provided.

The film forming chamber 201 is provided with an exhaust pipe connectedthrough main valve 210 to an exhaust pump, and the exhaust pipe isprovided with a subsidiary valve (not shown) serving to break the vacuumin the film forming chamber 201.

B indicates an active species transportation space doubling as anactivation space to generate an active species which has a mixing regionB' situated at the downstream side. The space B opens into the filmforming space A through nozzle means 213. 212 indicates a feed pipe foran active species raw material gas which is connected to the activespecies transportation space through circumferential wall D, which hasactive species raw material gas passage 202 formed by outer wall 203 andinner wall 204 having a plurality of gas feeding holes (not shown).

205 indicates a precursor transportation conduit being open at its endpositioned in the mixing region B'. The position of the opening (notshown) of the conduit 205 is about 7 cm distant from the nozzle means213. The conduit 205 has inner space C to which precursor raw materialfeed pipe 211 is connected.

206 indicates a microwave power source electrically connected to outerwall 203.

As the substrate 207, a polyamide film whose surface was made conductiveby depositing a layer of ITO in a thickness of 1000 A was used.

The polyamide substrate was treated with a 1% solution of NaOH, washedwith water, and then air-dried. This polyamide substrate wa then firmlyattached to the surface of the substrate holder 214 placed at apredetermined position in the film forming chamber 201. The air in thefilm forming chamber 201 and the active species transportation space Bwas evacuated by opening the main valve 210 to bring the chamber and thespace to a vacuum of about 1×10⁻⁶ Torr. Then the heater 208 wasactivated to uniformly heat the polyamide substrate 207 to about 200° C.and it was kept at this temperature.

At the same time, a gaseous mixture of H₂ and B₂ H₆ (B₂ H₆ /H₂ =3000ppm) as the active species raw material was fed at a flow rate of 5 SCCMinto the passage 202 and then into the space B through the gasliberation holes (not shown) of the inner wall 204, and a gaseousmixture of C₂ F₆ and SiF₄ as the precursor raw material was fed at aflow rate of 40 SCCM into the inner space C. After the flow rates o thetwo gases because stable, the vacuum in the film forming chamber 201 wasbrought to and kept at about 0.004 Torr by regulating the main exhaustvalve 210.

After the vacuum in the film forming chamber 201 became stable, themicrowave power source 206 was switched on to apply a discharge energyof 200 W into both the space B and the inner space C.

After this state was maintained for 5 minutes, there was formed a p-typea SiC (H, F) layer in a uniform thickness of 7000 A on the polyamidesubstrate.

After the formation of the p-type semiconductive layer was completed,application of the discharge energy was stopped and the introduction ofB₂ H₆ gas was terminated. Then the flow rates of the H₂ and SiF₄ gaseswere controlled to be 30 SCCM and 60 SCCM, respectively, the vacuum ofthe film forming chamber was brought to and kept at about 0.1 Torr byregulating the main exhaust valve 210, and a discharge energy of 300 Wwas applied.

After this state was maintained for 30 minutes, there was a formed anon-doped (intrinsic) semiconductive layer in a uniform thickness of 1.0μm on the previously formed layer.

Thereafter, a gaseous mixture of H₂ and PH₃ (PH₃ /H₂ =2000 ppm) as theactive species raw material was introduced at a flow rate of 10 SCCM,and SiH₄ gas as the precursor raw material was introduced at a flow rateof 30 SCCM.

Then, after the vacuum of the film forming chamber 201 was brought toand kept at about 0.04 Torr by regulating the main exhaust valve 210, adischarge energy of 200 W was applied.

After this state was maintained for 5 minutes, there was formed ann-type a Si:F:H layer in a uniform thickness of about 5000 A on thenon-doped semiconductive layer.

Finally, an aluminum electrode layer in a thickness of about 1000 A wasapplied to the n-type semiconductive layer as formed above by means of aknown vacuum evaporation deposition method thereby to obtain a PIN typephotovoltaic member.

As a result of evaluating the rectification characteristic andphotovoltaic effect of the resulting photovoltaic member by measuringthe I-V characteristics of the member (area: 1 cm²), the member wasdetermined to have a diode rectification ratio of 4×10² and a dioden-value of 1.3.

As for its photovoltaic characteristics, when light was radiated fromthe substrate side at about 100 mW/cm² of AMl radiation, a photoelectricconversion efficiency of more than 14% was obtained.

EXAMPLE 2

In accordance with the procedure described below, a photovoltaic memberwas prepared by using apparatuses as shown in FIG. 3 and FIG. 4.

FIGS. 3A and 3B are detailed schematic diagrams of one of the activationand transportation devices 407, 408, and 409 in the apparatus shown inFIG. 4.

In FIGS. 3A and 3B, 301 indicates an activation and transportation spacehaving mixing region 301' at its downstream side, which is formed bycircumferential wall 310 and two end walls 313 and 314. Thecircumferential wall 310 has active species raw material passage 312formed by surrounding outer wall 310 and inner wall 311 having aplurality of gas liberation holes (not shown). 304 indicates a feed pipefor an active species raw material gas provided with a flow ratecontrolling valve 305, feed pipe 304 being connected to the passage 312.302 indicates a conduit having space 302' doubling as a transportationspace for a precursor raw material gas and as a precursor generationspace, which is situated horizontally within the space 301. 307indicates a feed pipe for the precursor raw material provided with flowrate controlling valve 306, which is connected to the space 302'. 303indicates a microwave power source electrically connected to the outerwall 310. 308 indicates a narrowed passage for gas flow, which isrepresented by, for example, a nozzle, which connects with film formingspace A of film forming chamber 401 of the apparatus as shown in FIG. 4.

In FIG. 4, 407, 408, and 409 respectively indicate activation andtransportation devices as shown in FIG. 3. 402' indicates a substrate onsubstrate holder 402.

405 indicates a motor for rotating, lifting, and lowering the substrateholder 402 through rotary shaft 406. 403 indicates an infrared lamp forheating the substrate 402'.

404 indicates a mirror for reflecting infrared radiation toward thesubstrate 402'. The film forming chamber 401 is provided with exhaustpipe 410 connected through main exhaust valve 410' to a vacuum device(not shown). Subsidiary exhaust valves 411, 412, and 413 are connectedto the film forming chamber 401 to break the vacuum therein.

In this example, the activation and transportation devices 407, 408, and409 are used respectively for the formation of a n-type layer, theformation of a non doped layer, and the formation of a p-type layer.

A stainless steel plate of thickness 1.0 mm was used as the substrate402'.

After the substrate was cleaned in accordance with the procedurementioned in Example 1, it was firmly attached to the surface of thesubstrate holder 402, and the position of the substrate 402' was loweredto the level where the top of the substrate 402' was situated under theopening of the activation and transportation device 409 by the action ofthe rotary shaft 406. The air in the film forming chamber 401 and theactivation and transportation devices 407, 408, and 409 was exhausted byopening the subsidiary exhaust valves 411, 412, and 413 while the mainvalve 410' was closed, to bring their spaces to a vacuum of about 1×10⁻⁵Torr. Then, the infrared lamp was switched on to uniformly heat thesubstrate to about 290° C., the substrate being kept at thattemperature. Each of the gases as shown in Table 1 was fed into thecorresponding activation and transportation devices 407, 408, and 409 inaccordance with the corresponding conditions as shown in Table 1, andthe vacuum in the film forming space A was brought to and kept at about0.002 Torr by regulating the main exhaust valve 410'. Thereafter, themicrowave power source was switched on to apply a discharge energy ofcorresponding electric power as shown in Table 1 to each of theactivation and transportation devices 407, 408, and 409, respectively.

After the microwave discharge state in each of the activation andtransportation devices became stable, the substrate was lifted with aspeed of 2.4 mm/minute by the action of the rotary shaft 406. In thisway, there was formed firstly an n-type semiconductive layer in athickness of about 0.4 μm, secondly an i-type semiconductive layer in athickness of about 2.0 μm, and finally a p-type semiconductive layer ina thickness of about 0.5 μm, thereby to prepare a photovoltaic member.

It as evaluated that this member so produced has practically applicablecharacteristics as a photovoltaic member.

Moreover, no change in said characteristic was found even after lighterradiation of 100 mW for 24 hours.

In a comparative test wherein a photovoltaic member having a similarstructure to the above photovoltaic member which was prepared inaccordance with the known glow discharge manner using SiH₄ was used, itwas found that the photovoltaic member of this invention has aphotoelectric conversion efficiency of 2.5 times that of the latterphotovoltaic member.

                  TABLE 1                                                         ______________________________________                                                                       Micro-                                                                        wave  Film                                           Active species                                                                             Precursor   electric                                                                            forming                                        raw material(s)                                                                            raw material(s)                                                                           power rate                                     ______________________________________                                        Device                                                                              H.sub.2 : 10 SCCM                                                                          SiF.sub.4 : 20 SCCM                                                                       60 W  0.5 A/sec.                               407   (B.sub.2 H.sub.6                                                                           C.sub.2 F.sub.6 : 2 SCCM                                         1000 ppm added)                                                         Device                                                                              H.sub.2 : 30 SCCM                                                                          SiF.sub.4 : 30 SCCM                                                                       300 W   5 A/sec.                               408                                                                           Device                                                                              H.sub.2 : 100 SCCM                                                                         SiF.sub.4 : 30 SCCM                                                                       40 W  0.3 A/sec.                               409   (PH.sub.3 :                                                                   2000 ppm added)                                                         ______________________________________                                    

EXAMPLE 3

The procedures as mentioned in Example 1 were generally followed.

As the substrate, an n-type crystalline silicon plate (conductivity: 10ohm-cm) was used. The flow rates of H₂ and SiF₄ gases were controlled tobe 30 SCCM and 60 SCCM respectively, a microwave discharge energy of 300W was applied, the vacuum in the film forming chamber 201 was controlledto be about 0.1 Torr, and after 30 minutes' process operation in thisstate there was formed an a-Si:F:H layer in a thickness of about 1.0 μmon the silicon plate. Thereafter, N₂ gas was added to H₂ gas at a flowrate of 90 SCCM, the flow rate of SiF₄ was controlled to be 10 SCCM, amicrowave discharge energy of 300 W was applied, the vacuum in the filmforming chamber 201 was controlled to be 0.2 Torr and after 2 minutes'process operation in this state there was formed an a-SiN:F:H layer in athickness of about 700 A on the above a Si:F:H layer.

Finally, a Pd electrode layer in a thickness of about 50 A was formed onthe a-SiN:F:H layer by means of a known electron beam vapor depositionmethod thereby to prepare a photovoltaic member.

The photovoltaic characteristics of this member were examined and, as aresult, it was found that this member has a photoelectric conversionefficiency of 1.5 times that of a Schottky type solar cell having asimilar structure to the above member, which was prepared in accordancewith the known glow discharge method using SiH₄ gas.

What we claim is:
 1. An apparatus for the preparation of a photoelectricconversion layer for a photoelectromotive force member comprising:(a) afilm-forming chamber having an inner space in which a substrate holderfor a substrate is provided; (b) an exhaust pipe connected to saidfilm-forming chamber and through a main valve to an exhaust pump; (c) aconcentric triplicate conduit connected through a nozzle means to saidfilm forming chamber; said concentric triplicate conduit comprising:(i)an outer passage for introducing a gaseous raw material and being formedby a circumferential wall and an inner wall having a plurality of gasliberation holes; (ii) a middle passage for applying microwave energy tosaid gaseous raw material to generate an active species and having amixing region at the downstream side before the nozzle means, and (iii)a central passage situated horizontally within said middle passage (ii)for introducing a gaseous precursor and for transporting said gaseousprecursor toward the film-forming chamber and being open at an endpositioned in the mixing region and leaving a predetermined distance tothe nozzle means; said middle passage (ii) being formed by the innerwall of said outer passage and a circumferential wall of the centralpassage (iii); (d) a feed pipe for introducing said gaseous raw materialto said outer passage (i); (e) a microwave power source for generatingsaid microwave energy; and (f) a feed pipe for introducing said gaseousprecursor to said central passage (iii).
 2. The apparatus according toclaim 1, wherein said predetermined distance is 0.1 to 200 mm.
 3. Theapparatus according to claim 1, wherein the film-forming chamber isprovided with a plurality of said concentric triplicate conduits.
 4. Theapparatus according to claim 1, wherein the substrate holder is providedwith a rotary shaft connected to a motor to rotate, lift and lower thesubstrate.
 5. The apparatus according to claim 1, wherein means to applylight or heat energy to the inner space is provided.
 6. The apparatusaccording to claim 5, wherein said means comprises an infrared lamp. 7.The apparatus according to claim 5 wherein said infrared lamp isprovided with a mirror for reflecting infrared radiation toward thesubstrate.